Epitaxial MoN x layers deposited on MgO(001) by reactive magnetron sputtering in 20 mTorr N 2 at T s = 600-1000 °C exhibit a cubic rock-salt type structure, a N-to-Mo ratio that decreases from x = 1.25-0.69 with increasing T s , and a lattice constant that simultaneously decreases from 4.26-4.16 Å. A combination of composition, thickness, lattice-constant, and atomic area-density measurements indicate that the rock-salt structure contains both anion and cation vacancies, with the Mo site occupancy Χ Mo decreasing from 0.89±0.06 to 0.70±0.04 while the N site occupancy Χ N increases from 0.60±0.04 to 0.88±0.04, as x increases from 0.69-1.25. Density functional calculations for over 200 cubic MoN x configurations confirm the energetic stability of both cation and anion vacancies and predict Χ Mo to decrease from 1.00 to 0.67 for x = 0.54-1.50, while Χ N increases from 0.50 to 1.00 for x = 0.50-1.36. The simulations are in good agreement with experiments and indicate a preference for a 75% site occupancy on both sublattices for compositions near stoichiometry, with Χ Mo = 0.75 for x = 1.00-1.22 and Χ N = 0.75 for x = 0.86-1.00. Correspondingly, cubic stoichiometric MoN is most stable in the NbO structure.